EP0266410B1 - Aufzeichnungselemente mit hydrophilen schichten, die hydrophobe in polymerteilchen enthalten, und methode zu ihrer herstellung - Google Patents

Aufzeichnungselemente mit hydrophilen schichten, die hydrophobe in polymerteilchen enthalten, und methode zu ihrer herstellung Download PDF

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EP0266410B1
EP0266410B1 EP87903494A EP87903494A EP0266410B1 EP 0266410 B1 EP0266410 B1 EP 0266410B1 EP 87903494 A EP87903494 A EP 87903494A EP 87903494 A EP87903494 A EP 87903494A EP 0266410 B1 EP0266410 B1 EP 0266410B1
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percent
hydrophobe
hydrophilic
weight
weight percent
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EP0266410A1 (de
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Robert H. Fehnel
Paul Mitacek
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein

Definitions

  • This invention relates to imaging elements, including radiation-sensitive elements such as photographic color paper products.
  • radiation-sensitive elements such as photographic color paper products.
  • it relates to such elements having a hydrophilic layer which contains a hydrophobic compound (e.g. optical brightener) uniformly distributed in polymeric particles.
  • This invention also relates to a method of making such elements.
  • hydrophobes hydrophobic compounds
  • non-polymeric compounds such as color-forming couplers, ultraviolet light absorbing materials, optical brighteners, etc.
  • hydrophilic binder materials in the manufacture of radiation-sensitive products.
  • One of the simplest of these techniques involves mechanically dispersing the hydrophobe in solid or liquid form in the binder material by passing a blend of the hydrophobe and binder material several times through a high energy mill. This technique, however, generally produces unsuitable dispersions which are often unstable.
  • hydrophobe Depending upon the hydrophobe, sometimes only a limited amount of hydrophobe can be successfully "loaded” into latex particles, and any residual hydrophobe must be removed to prevent deleterious image effects. Often some of the hydrophobe "leaches" out of the latex particles and forms “crystals". Such crystals deleteriously affect image quality (e.g. reduce sharpness) and, when clumped together, reduce layer smoothness which is important for very thin coatings. This leached-out hydrophobe can also wander into adjacent layers, causing additional problems.
  • U. S. Patent 3,418,127 discloses a method of finely dispersing fluorescent compounds in latex particles by mixing the fluors in polymerizable monomers and emulsion polymerizing the monomers having the fluors therein.
  • the resulting latex purportedly can be coated and dried to form a thin film, preferably over the radiation-sensitive layers of a photographic element.
  • West German Patent 2,509,342 published September 11, 1975 teaches the incorporation of optical brighteners into polymeric particles by dissolving the optical brighteners in polymerizable monomers and emulsion polymerizing the monomers.
  • Emulsion polymerization proceeds in micelles formed by water-soluble surfactant.
  • the resulting latex is purportedly mixed with a compatible colloid (e.g. gelatin) and coated either with a photographic emulsion or in a separate layer in a photographic element.
  • a compatible colloid e.g. gelatin
  • the aforesaid U. S. Patent 4,584,255 which is directed to the objective of providing hydrophobe-containing compositions which can be coated to provide substantially crystal- and agglomeration-free hydrophilic layers, provides an important advance in this art.
  • the monomers containing the hydrophobe are dispersed in an aqueous medium and allowed to polymerize as a suspension of fine monomer droplets.
  • This technique avoids the problems encountered with emulsion polymerization of hydrophobe-containing monomers. For example, in an emulsion polymerization process, monomer having hydrophobe dissolved therein must migrate through water and cross the interface of latex micelles. During such migration, the monomer tends to migrate faster than the hydrophobe.
  • an element comprises a support having thereon a substantially crystal- and agglomeration-free hydrophilic layer.
  • This layer comprises a hydrophilic composition containing a hydrophilic binder and water-insoluble polymer particles dispersed therein. These particles have recurring units derived from a monomeric composition composed of one or more ethylenically unsaturated polymerizable monomers with more than about 5 percent and up to 100 percent by weight of the monomeric composition consisting of at least one ethylenically unsaturated polymerizable monomer having a crosslinkable moiety, and comprise at least about 0.5 percent by weight of a hydrophobe uniformly distributed throughout.
  • the present invention differs in a critical manner from the invention of the aforesaid U. S. Patent 4,584,255 in that it requires the use of from more than about 5 up to 100 weight percent of an ethylenically unsaturated polymerizable monomer having a crosslinkable moiety.
  • the use of an ethylenically unsaturated monomer having a crosslinkable moiety is optional and, when such monomer is employed, it is used in amounts of less than about 5 weight percent, as compared with the more than about 5 up to 100 weight percent required in the present invention.
  • the elements of this invention are radiation-sensitive elements (e.g., color photographic paper products) which have the hydrophilic layer described above located between the support and the radiation-sensitive layer(s).
  • the hydrophobe in this embodiment is usually an optical brightener.
  • This invention also comprises a method of making the element described hereinabove.
  • the steps of this method comprise:
  • a radiation-sensitive composition is applied over the hydrophilic layer formed in step (d).
  • the hydrophobe useful in the practice of this invention is a compound which is essentially insoluble in distilled water at 25°C.
  • the dissolved concentration of hydrophobe in water under these conditions is less than about 0.5 weight percent, based on the weight of the water.
  • Any such hydrophobe can be used in the practice of this invention as long as it can be dissolved or uniformly dispersed in the monomeric composition to be used in making the polymer particles described hereinbelow.
  • the hydrophobe is soluble in the monomeric composition at a concentration of at least about 8 weight percent, based on the total monomer weight.
  • hydrophobes examples include, but are not limited to, photographic dyes; photographic dye-forming couplers; photographic developing agents or other photographic addenda; optical brighteners; ultraviolet light absorbing compounds; and others known to one skilled in the photographic art.
  • Specific photographic addenda which can act as hydrophobes include those compounds used to perform coupling, silver halide development, oxidized developer scavenging, absorbtion of light of certain wavelengths, spectral sensitizing or desensitizing, or diffusion transfer dye- image-forming. Examples of such hydrophobes are listed in considerable detail in U. S.
  • Patent 4,203,716 (noted hereinabove), the disclosure of which is incorporated herein by reference in its entirety; and in Research Disclosure, publications 15162 (November, 1976) and 17643 (December, 1978), paragraphs III, IV, VI, VII and VIII (Research Disclosure is published by Kenneth Mason Publications Limited, Emsworth, Hampshire, P010 7DD, United Kingdom). Mixtures of hydrophobes can be used if desired.
  • optical brighteners include such classes of compounds as: oxazoles; oxadiazoles, including benzoxazoles; imidazoles, including benzimidazoles; pyrazolines; coumarins; stilbenes; triazines; imidazolones; naphthotriazoles; acetylenes; vinylene compounds; and others known to a skilled worker in the art.
  • Specific examples of such optical brighteners are described in Research Disclosure, publication 17643, paragraph V, noted hereinabove, U. S. Patent 3,666,680 (issued May 30, 1972 to Briggs) and W. German OLS 2,509,342, noted hereinabove, the disclosures of which are incorporated herein by reference to illustrate optical brighteners useful in this invention.
  • optical brighteners Of the many classes of optical brighteners which can be used in the practice of this invention, the stilbene and naphthotriazole compounds are preferred, with such brighteners as Uvitex OB T ⁇ ", Tinopal PCRTM and Tinopal SFG T " being particularly useful. These optical brighteners are commercially available from Ciba-Geigy, Ardsley, New York.
  • the amount of hydrophobe in the polymer particles can be varied widely depending upon intended use, but it must be at least about 0.5 weight percent and is preferably from about 0.5 to about 10 weight percent, and more preferably from about 5 to about 10 weight percent.
  • the polymer particles useful in the practice of this invention are formed from a monomeric composition composed of one or more ethylenically unsaturated polymerizable monomers, at least one of which must have a crosslinkable moiety.
  • the lower limit for the amount of ethylenically unsaturated polymerizable monomer having a crosslinkable moiety is more than about 5 percent by weight, and preferably it is at least about 10 percent by weight.
  • the upper limit is 100 percent by weight.
  • the monomeric composition comprises about 50 to about 90 weight percent of at least one ethylenically unsaturated polymerizable monomer, and about 10 to about 50 weight percent of at least one ethylenically unsaturated polymerizable monomer having a crosslinkable moiety. Most preferably, the monomeric composition comprises about 75 to about 90 weight percent of at least one ethylenically unsaturated polymerizable monomer, and about 10 to about 25 weight percent of at least one ethylenically unsaturated polymerizable monomer having a crosslinkable moiety.
  • Patent 4,584,255 by utilizing less than about 5 weight percent of monomer having a crosslinkable moiety, after only a few weeks of storage, significant quantities of the hydrophobe can be found to have migrated out of the polymer and crystallized in the surrounding water phase. It is believed that this can be explained by the relatively slow reaction rate of the monomer system allowing hydrophobe molecules to move out of the way of the multiplying polymer chains. As a result, there is a high concentration of hydrophobe near the surface of the polymer particle, and, with time, some of this hydrophobe migrates into the water phase.
  • the key to the success of the present invention is believed to be gelation at a low degree of monomer conversion, so that the hydrophobe is "trapped" at a stage in the polymerization process where there is still ample unpolymerized monomer to keep the hydrophobe in solution.
  • the result is a highly uniform distribution of the hydrophobe throughout the polymer particle and little or no tendency for the hydrophobe to migrate.
  • the water-insoluble polymeric particles useful in this invention comprise polymers characterized by the structure: where -A- represents randomly recurring units in the polymer chain derived from one or more vinyl aromatics; vinyl esters; olefins, diolefins; or esters of a, (3-unsaturated polymerizable carboxylic acids.
  • vinyl aromatics include styrene, a-methylstyrene, p-bromostyrene, o-chlorostyrene, 2- vinylmesitylene, 1-vinylnaphthalene, m- and p-vinyltoluene, 3,4-dichlorostyrene and the like.
  • Useful vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate and the like.
  • useful esters of a, ⁇ -unsaturated polymerizable carboxylic acids include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, methyl a-bromoacrylate, 4-chlorobutyl acrylate, cyclohexyl acrylate, 2-norbornylmethyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, 2-ethoxyethyl methacrylate, 3-chloropropyl acrylate, 2-2-dimethylbutyl acrylate, and the like.
  • Useful olefins and diolefins include, for example, ethylene, propylene, 1,3-butadiene, isoprene, chloroprene, cyclopentadiene, 5-methyl-1,3,6-heptatriene, and the like.
  • -A- represents randomly recurring units derived from one or more vinyl aromatics, e.g., styrene, or esters of ⁇ - ⁇ -unsaturated polymerizable carboxylic acids, e.g., methyl methacrylate, butyl acrylate and tetrahydrofurfuryl methacrylate. More preferably, -A- is derived from styrene or methyl methacrylate or both.
  • -B- represents randomly recurring units in the polymer chain derived from one or more ethylenically unsaturated polymerizable monomers having one or more anionic moieties, e.g., sulfo, phosphono or carboxy moieties (including alkali metal or ammonium salts thereof). These recurring units contribute to the dispersibility of the polymer particles in hydrophilic binders.
  • Examples of useful monomers having such anionic moieties include 4-acryloyloxybutane-1-sulfonic acid, sodium salt; 3-acryloyloxy-1-methylpropane-1-sulfonic acid, sodium salt; acrylic and metbacrylic acids and alkali metal salts thereof; m- and p-styrenesulfonic acid and alkali metal salts thereof; 3-methacryloyloxypropane-1-sulfonic acid, sodium salt; lithium methacrylate, N-[3-(N-phenylsulfonyl-N-sodiosulfamoyl)phenyl]acrylamide, N-[2-(N-methylsulfonyl-N-potassiosulfamoyl)ethyl]methacrylamide, ammonium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, sodium salt, and the like.
  • -B- represents randomly recurring units derived from one or more monomers having sulfo or carboxy moieties, such as styrenesulfonic acids or alkali metal salts thereof, acrylic acid, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid. More preferably, -B- is derived from styrenesulfonic acids or salts thereof.
  • -C- represents randomly recurring units in the polymer chain derived from one or more ethylenically unsaturated polymerizable monomers having crosslinkable moieties. Such units contribute to the water-insolubility of the resulting polymer. They also make the polymer less soluble in organic solvents generally used in coating operations and thereby reduce the tendency of the hydrophobe to wander.
  • These monomers have two or more ethylenically unsaturated moieties which crosslink during polymerization (e.g., diacrylates, divinylbenzene, etc.). Alternatively, they can also have moieties which do not react to provide crosslinking during polymerization, but provide a post-polymerization crosslinking because of reaction with a hardener or with another moiety on a different monomer.
  • Such monomers include, for example, 2-acetoacetoxyethyl methacrylate, N-(2-acetoacetoxyethyl)acrylamide, N-(2-acetoacetamidoethyl)acrylamide and 2-aminoethyl methacrylate hydrochloride.
  • Monomers having two or more ethylenically unsaturated sites available for reaction include, for example, diacrylates; dimethacrylates; triacrylates; trimethacrylates; divinyl compounds; and the like.
  • Examples of such monomers include divinylbenzene, ethylene dimethacrylate, 2,2-dimethyl-1,3-propylene diacrylate, propylidene dimethacrylate, 1,6-hexamethylene diacrylate, phenylethylene dimethacrylate, tetramethylene dimethacrylate, 2,2,2-trichloroethylidene dimethacrylate, ethylenebis(oxyethylene)diacrylate, oxydiethylene diacrylate, ethylidyne trimethacrylate, allyl acrylate, vinyl allyloxyacetate, 1-vinyloxy-2- allyloxyethane, 2-crotonoyloxyethyl methacrylate, diallyl phthalate, triallyl cyanurate,
  • -C- represents randomly recurring units derived from one or more diacrylates or dimethacrylates, e.g., ethylene diacrylate or ethylene dimethacrylate or both, or from divinyl compounds, e.g., divinylbenzene.
  • the polymers useful in the practice of this invention can also comprise minor amounts (typically less than about 5 weight percent) of randomly recurring units in the polymer chain derived from one or more ethylenically unsaturated polymerizable monomers other than those described for -A-, -B- or -C-hereinabove. Generally, these units are present in very small amounts in the polymer chain so as not to deleteriously affect polymer water insolubility or other desirable polymer properties.
  • vinyl amides e.g., acrylamide, methacrylamide, N-isopropylmethacrylamide, methacrylamide, N-isopropylmethacrylamide, N-isopropylacrylamide, N-(3,6-dithiaheptyl)-acrylamide, etc.
  • vinyl nitriles e.g., acrylonitrile, methacrylonitrile, 3-butenenitrile, etc.
  • vinyl ketones e.g., methyl vinyl ketone, diacetone acrylamide, etc.
  • vinyl halides e.g., vinyl chloride, vinyl bromide, vinylidene chloride, etc.
  • vinyl ethers e.g., allyl methyl ether, allyl phenyl ether, 2-chlorovinyl methyl ether, etc.
  • N-vinylsuccinamide N-vinylphthalimide
  • N-vinylpyrazolidinone and others known
  • the proportions of the various units of the polymer structure defined herein are as follows: w represents a weight percent of from 0 to about 90, x represents a weight percent of from 0 to about 20, and y represents a weight percent of from about 10 to 100. All weight percentages are based on total monomer weight.
  • w represents a weight percent of from about 50 to about 90
  • x represents a weight percent of from 0 to about 20
  • y represents a weight percent of from about 10 to about 50.
  • w represents a weight percent of from about 75 to about 90
  • x represents a weight percent of from 0 to about 20
  • y represents a weight percent of from about 10 to about 25.
  • w is from 75 to 85 weight percent
  • x is from 0 to 5 weight percent
  • y is from 15 to 25 weight percent.
  • the glass transition temperature (Tg) of the polymers useful in the practice of this invention can be varied widely, they generally have a glass transition temperature (Tg) greater than about 70°C, and preferably in the range of from about 90 to about 120°C, in order to prevent diffusion of hydrophobe into the coated layers during drying and storage and to improve compatibility with coating addenda.
  • the glass transition temperature can be determined by any convenient method suitable for this purpose. For example, one such method is differential scanning calorimetry as described in Techniques and Methods of Polymer Evaluation. Volume 2, Marcel Dekker, Inc., New York, N. Y., 1970.
  • polymers useful in the practice of this invention include:
  • the polymer particles useful in the practice of this invention are generally prepared by addition polymerization of the monomers in an aqueous suspension. This is commonly known as “suspension polymerization”. It can be carried out in batch, semi-continuous or continuous operations, as is well known in the art.
  • Particularly preferred polymers for the purpose of this invention are copolymers of styrene and divinylbenzene.
  • a monovinylic monomer such as styrene and a bi-unsaturated comonomer such as divinylbenzene
  • Hild and Okasha "Kinetic Investigation Of The Free Radical Crosslinking Copolymerization In The Pre-gel State", Makromol. Chem. 186 93-110 (1985).
  • the method of this invention includes dissolving the hydrophobe(s) in solution with the ethylenically unsaturated polymerizable monomers.
  • the monomer solution is then dispersed as fine droplets in water and subjected to conditions sufficient to promote suspension polymerization of the monomers.
  • one or more polymerization initiators to initiate polymerization and promote its completion. At least one of the initiators, if used, is oleophilic and is dissolved in the monomers along with the hydrophobe.
  • Useful oleophilic initiators include azo compounds, such as the VAZO" initiators commercially available from DuPont, Wilmington, Delaware, e.g., VAZO-64 T "' which is 2,2'-azobis(2-methylpropionitrile), VAZO-52 T “' which is 2,2'-azobis(2,4-dimethylvaleronitrile), VAZO-33 T “' which is 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) and VAZO-67TM which is 2,2'-azobis(2-methylbutanenitrile); peroxides, such as lauroyl peroxide and benzoyl peroxide; and others known to one skilled in the art.
  • Water-soluble polymerization initiators can be used in addition to oleophilic initiators as long as there is sufficient oleophilic initiator to initiate the polymerization of the suspended monomer droplets and an insubstantial amount of emulsion polymerization occurs.
  • One or more surface active agents are also often employed in suspension polymerization to aid in keeping the dispersed monomer droplets from clumping together in the aqueous medium.
  • At least one of the surfactants, if used, is oleophilic and is incorporated into the reaction mixture by dissolving it in the monomer(s) along with the hydrophobe.
  • the temperature of the monomers is maintained at greater than room temperature (20-25°C), but less than the temperature at which the monomers undergo spontaneous polymerization (this varies with the monomer(s) and initiators used). Generally, the temperature used to this purpose is in the range of from about 30 to about 45°C.
  • the resulting solution is dispersed in water as fine droplets and subjected to pressure and temperature conditions suitable for polymerization of the monomers in the suspended droplets and formation of small, suspended polymer particles.
  • the monomer solution is generally present in droplet form in this dispersion in a range of from about 20 to about 50 percent, based on total dispersion weight.
  • the pressure employed in the polymerization is generally only that needed to maintain the reaction mixture in liquid form, and is usually atmospheric pressure.
  • the polymerization temperature is subject to wide variation as it depends upon several variables including the monomer, initiator and weight percent of monomers in the dispersion. However, generally the temperature is in the range of from about 20°C to about 120°C, and preferably from about 50 to about 70°C. The temperature can vary during the polymerization reaction because of the evolution of heat from the reaction itself.
  • the monomer solution can be dispersed in the aqueous medium prior to polymerization in any suitable manner which may depend upon the polymerization technique (batch, continuous or semi-continuous) employed.
  • the solution is dispersed in the aqueous phase by any means which produces high shear sufficient to form very fine droplets containing monomer, hydrophobe and preferably, oleophilic initiator and surfactant.
  • dispersing can be accomplished by mechanical means such as high-speed stirring or vigorous agitation of some manner, or by pumping a monomer-water mixture through a small orifice or high shear mill into a reactor vessel.
  • the resulting polymer is in the form of small particles, the size of which can be varied by changing the dispersing conditions or amount of surfactant.
  • the average particle size is generally in the range of from about 0.1 to about 20 microns, with polymer particles in the range of from about 0.4 to about 1 microns being particularly useful in the preferred embodiment of this invention utilizing optical brighteners as the hydrophobe.
  • the resulting aqueous suspension of polymeric particles can be used directly after polymerization. Water may be removed, if desired, to increase the percent solids of the suspension.
  • the polymeric suspension is then uniformly dispersed in one or more hydrophilic binder materials, or "vehicles” as they are often called in the art, to form a hydrophilic composition.
  • hydrophilic binder materials or "vehicles” as they are often called in the art, to form a hydrophilic composition.
  • Such binders act as peptizers for the polymeric particles to reduce their tendency to settle.
  • Suitable hydrophilic binders include both naturally-occurring substances, such as proteins (e.g., gelatin, gelatin derivatives, cellulose derivatives), polysaccharides (e.g., dextran), gum arabic, etc.; and synthetic polymeric substances such as water-soluble polymers (e.g., poly(vinyl alcohol), acrylamide polymers, poly(vinyl pyrrolidones), etc.), and others known to one skilled in the art, as described, for example, in Research Disclosure, publication 17643, noted hereinabove, paragraph IX. Gelatin is a preferred binder in the practice of this invention.
  • proteins e.g., gelatin, gelatin derivatives, cellulose derivatives
  • polysaccharides e.g., dextran
  • gum arabic etc.
  • synthetic polymeric substances such as water-soluble polymers (e.g., poly(vinyl alcohol), acrylamide polymers, poly(vinyl pyrrolidones), etc.), and others known to
  • the polymeric particles are present within a binder in an amount of at least about 15, and preferably from about 20 to about 70 percent, based on total dry weight of hydrophilic composition. This corresponds to a coating coverage of polymeric particles of at least about 20 mg/m 2 of coated surface area. Particles of different polymers containing the same or different hydrophobes can be used in the same hydrophilic composition, if desired.
  • the resulting hydrophilic composition can be purified, if desired, in any suitable manner to remove any unwanted addenda.
  • the described hydrophilic composition can be applied to a suitable substrate, such as a conventional support, using conventional techniques to provide an element having a hydrophilic layer. Additional compositions can be applied simultaneously or subsequently to form additional layers over or under the hydrophilic layer. It is specifically contemplated to apply these compositions to a support using coating hoppers or other coating apparatus conventionally employed in preparing single or multiple layer radiation-sensitive elements.
  • Useful coating and drying techniques and supports e.g., paper, polymeric films, glass, etc. are described, for example, in Research Disclosure, publication 17643, noted hereinabove, paragraphs XV and XVII.
  • the hydrophilic compositions described herein can be used in radiation-sensitive elements of various types. Generally, the coating coverage of the hydrophilic composition depends upon its use and the type of element it is incorporated into.
  • Radiation-sensitive elements of this invention include, for example, image transfer materials, lithographic materials, physical development materials, radiographic materials, dry development materials, negative- and positive-working color-forming materials (including color films and color photographic papers), black-and-white films and papers, and the like. The details of such materials are well known in the art and are described, for example, in Research Disclosure, publication 17643, noted hereinabove.
  • the described hydrophilic compositions are useful in multilayer color photographic paper products having a resin-coated photographic paper support and a plurality of color-forming silver halide emulsion layers coated thereon.
  • the hydrophilic compositions can be used in any location in the radiation-sensitive elements of this invention, including within the radiation-sensitive layers themselves. Preferably, however, they are coated as individual hydrophilic layers, above, below or in between radiation-sensitive layers.
  • the hydrophilic composition contains an optical brightener as the hydrophobe and is incorporated between the support and the radiation-sensitive layer(s) to provide an optical brightener layer.
  • the most preferred embodiment of the present invention is photographic color paper comprised of a paper support having a polyethylene layer on each side thereof and a hydrophilic layer of this invention between the polyethylene layer and the overlying silver halide emulsion layers.
  • the hydrophilic layer serves as a reflective layer which is commonly referred to as a "white rug”.
  • the hydrophilic layer which functions to provide improved sharpness and reduced Dmi,,, comprises the following ingredients:
  • Hollow polymeric beads of any type may be employed as long as they perform the desired function.
  • Particularly useful hollow polymeric beads are core/sheath polymeric particles adapted to serve as an extender for inorganic pigments. These are well known materials and are described, for example, in United States Patents 4,427,836, 4,468,498, and 4,469,825.
  • a preferred material is manufactured by Rohm and Haas Company, and sold under the trademark ROPAQUE OP-84. This material is described as being hollow spheres of an aqueous acrylic copolymer emulsion with an outside diameter of approximately 0.5 - 0.6 microns and an inner void-diameter of approximately 0.3 microns. As supplied, the beads appear as a milky white liquid, are approximately 40% solids by weight, and have a pH of 9 - 10.
  • the preferred inorganic pigment is titanium dioxide and the preferred optical brightener is 2,5-bis(6-butyl-2-benzoxazolyl)thiophene.
  • a hydrophilic layer prepared in accordance with the principles of this invention as a so-called "white rug" in a photographic color paper, it is important that the optical brightener be incorporated in the polymer at as high a concentration as is feasible.
  • the polymer merely serves as a carrier for the optical brightener so that high concentrations of optical brightener mean less of the carrier is required, which results in a thinner coated layer and consequent improvement in the sharpness of the color paper.
  • the optical brightener can be incorporated at a high concentration level, e.g., 8 to 10 percent by weight, yet it remains in the amorphous state in the polymer particles. This is important since, in its crystallized form it is not effective for the purposes for which it is incorporated in photographic reflection print materials, that is, for the purposes of providing improved sharpness and reduced D min .
  • Styrene (14.4 kg) and divinylbenzene (6.2 kg) were added to a water-jacketed 75-liter holding tank and warmed to 30°C.
  • the divinylbenzene was commercial grade material containing about 55% divinylbenzene, i.e., a total of about 3.4 kg of pure divinylbenzene, with the remainder being primarily ethyl vinyl benzene.
  • the pure divinylbenzene constituted 16.5% by weight of the monomeric composition.
  • the holding tank was pressurized with nitrogen and the contents were forced through an APV Gaulin Model 2F colloid mill into the reactor over a twenty-minute period.
  • the reaction was allowed to proceed for four hours at 70°C and the reaction mixture was then heated to 80°C and reacted for an additional five hours, whereupon it was cooled to 25°C.
  • the product was filtered through a three micron filter.
  • the storage stability of the polymer suspension was evaluated over a period of twenty-four weeks, and compared with the stability of an otherwise identical suspension which had been prepared using 2% by weight of divinylbenzene rather than the 16.5% by weight used in the above example. Stability was determined by viewing the water phase of the suspension under a microscope and counting the crystals of optical brightener present therein. The results obtained are summarized in the table below in which each of the values reported represents the average of several measurements.
  • the number of crystals formed in the suspension prepared from the 16.5% by weight divinylbenzene composition is much less than the number formed in the suspension prepared from the 2% by weight divinylbenzene composition.
  • the suspension prepared from the 16.5% by weight divinylbenzene composition was combined with gelatin, titanium dioxide, and a core/sheath polymer of the type described in United States Patent 4,427,836.
  • This composition provided excellent results when used to form a reflective layer, positioned between the polyethylene-coated paper support and the emulsion layers of a photographic reflection print material of the type described, for example, in Research Disclosure, publication 17643, noted hereinabove.

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Claims (25)

1. Element mit einem Träger, auf dem sich eine praktisch kristall- und agglomerationsfreie hydrophile Schicht befindet, die eine hydrophile Zusammensetzung mit einem hydrophilen Binder und hierin dispergierten wasserunlöslichen Polymerteilchen aufweist, wobei die Polymerteilchen (1) wiederkehrende Einheiten enthalten, die sich von einer Monomerenzusammensetzung ableiten, die zusammengesetzt ist aus einem oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren und (2) mindestens 0,5 Gew.-% eines gleichförmig verteilten Hydrophoben enthält, wobei die Monomerenzusammensetzung in Gegenwart des Hydrophoben polymerisiert worden ist,
dadurch gekennzeichnet, daß mehr als 5 Gew.-% und bis zu 100 Gew.-% der Monomerenzusammensetzung aus mindestens einem ethylenisch ungesättigten polymerisierbaren Monomer mit einer quervernetzbaren Gruppe bestehen und das Monomer während der Polymerisation quervernetzt wird.
2. Element nach Anspruch 1, das weiterhin eine oder mehrere strahlungsempfindliche Schichten enthält.
3. Element nach Anspruch 1 oder 2, in dem die hydrophile Schicht zwischen dem Träger und der oder den strahlungsempfindlichen Schicht(en) angeordnet ist.
4. Element nach Ansprüchen 1 bis 3, bestehend aus einem mehrschichtigen farbphotographischen Element mit einem Papierträger, auf dem sich eine Mehrzahl von photographischen, farbbildenden Silberhalogenidemulsionsschichten befindet.
5. Element nach Ansprüchen 1 bis 4, in dem die Polymerteilchen durch die Struktur
Figure imgb0004
gekennzeichnet ist, in der -A- für willkürlich verteilte, wiederkehrende Einheiten steht, die sich von einer oder mehreren vinylaromatischen Verbindungen, Olefinen, Diolefinen, Vinylestern oder Estern von a, β-ungesättigten polymerisierbaren Carbonsäuren ableiten, -B- für willkürlich verteilte, wiederkehrende Einheiten steht, die sich von einer oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren mit einer oder mehreren anionischen Gruppen ableiten; -C- für willkürlich verteilte wiederkehrende Einheiten steht, die sich von einem oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren mit einer quervernetzbaren Gruppe ableiten und w für 0 bis 90 Gew.-%; x für 0 bis 20 Gew.-% und y für 10 bis 100 Gew.-%, jeweils auf das Gesamtmonomerengewicht bezogen, stehen.
6. Element nach Anspruch 5, in dem w für 50 bis 90 Gew.-%, x für 0 bis 20 Gew.-% und y für 10 bis 50 Gew.-% stehen.
7. Element nach Anspruch 5, in dem w für 75 bis 90 Gew.-%, x für 0 bis 20 Gew.-% und y für 10 bis 25 Gew.-% stehen.
8. Element nach Anspruch 5, in dem -A- für willkürlich, wiederkehrende Einheiten steht, die sich von einer oder mehreren vinylaromatischen Verbindungen oder Estern von a, ß-ungesättigten polymerisierbaren Carbonsäuren ableiten; -B- für willkürlich verteilte wiederkehrende Einheiten steht, die sich von einem oder mehreren Monomeren mit einem oder mehreren Monomeren mit einem oder mehreren Sulfo- oder Carboxyresten ableiten und -C- für willkürlich verteilte, wiederkeherende Einheiten steht, die sich von einem oder mehreren Diacrylaten oder Dimethacrylaten ableiten.
9. Element nach Anspruch 5, in dem die Polymerteilchen aus Poly(methylmethacrylat-co-styrol-co-Ethylendimethacrylat) aufgebaut sind.
10. Element nach Anspruch 5, in dem die Polymerteilchen aus Poly(styrol-co-divinylbenzol) aufgebaut sind.
11. Element nach Anspruch 10, in dem die polymerteilchen wiederkehrende Einheiten aufweisen, die sich von einer Monomerenzusammensetzung ableiten, die zu etwa 75 bis etwa 90 Gew.-% aus Styrol und zu etwa 10 bis etwa 25 Gew.-% aus Divinylbenzol besteht.
12. Element nach Ansprüchen 1 bis 11, in dem das Hydrophob ein photographischer Farbstoff, ein einen photographischen Farbstoff bildender Kuppler; eine photographische Entwicklerverbindung; ein optischer Aufheller oder eine UV-Licht absorbierende Verbindung ist.
13. Element nach Anspruch 12, in dem das Hydrophob ein optischer Aufheller vom Oxazol-, Oxadiazol-, Imidazol-, Pyrazolin-, Coumarin-, Stilben-, Triazin-, lmidazolon-, Naphthotriazol-, Acetylen- oder Vinylentyp ist.
14. Element nach Ansprüchen 1 bis 13, in dem das Hydrophob in den Polymerteilchen in einer Menge von 0,5 bis 10 Gew.-% vorliegt.
15. Element nach Ansprüchen 1 bis 14, in dem die Polymerteilchen in dem Binder in einer Menge von mindestens 15%, bezogen auf das Gesamtgewicht der trockenen Zusammensetzung, dispergiert sind.
16. Element nach Anspruch 15, in dem der Binder aus Gelatine besteht.
17. Element nach Ansprüchen 4 bis 16, in dem die hydrophile Schicht zusätzlich hohle Polymerkügelchen und Titandioxid enthält.
18. Element nach Ansprüchen 4 bis 17, in dem die hydrophile Schicht Gelatine, hohle Polymerkügelchen, Titandioxid und Teilchen aus einem Polymer mit wiederkehrenden Einheiten enthält, die sich von einer Monomerenzusammensetzung ableiten, die zu 75 bis 90 Gew.-% aus Styrol und zu 10 bis 25 Gew.-% aus Divinylbenzol aufgebaut ist, wobei die Teilchen 5 bis 10 Gew.-% gleichförmig verteiltes, 2,5-Bis(6-butyl-2-benzoxazolyl)thiophen enthalten.
19. Verfahren zur Herstellung eines Elementes mit einem Träger, auf dem sich eine praktisch kristall-und agglomerationsfreie hydrophile Schicht befindet, und die Schicht eine hydrophile Zusammensetzung aufweist, die einen hydrophilen Binder und hierin dispergierte wasserunlösliche Polymerteilchen enthält, mit den Stufen:
(a) Lösen von mindestens 0,5%, bezogen auf das Gesamtmonomerengewicht, eines Hydrophoben in Lösung mit einer Monomerenzusammensetzung, aufgebaut aus einem oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren;
(b) Dispergieren der Lösung in Wasser in Form feiner Tröpfchen unter Bedingungen, die ausreichen, um die Polymerisation der Monomeren in den Tröpfchen zu fördern und um polymerteilchen zu bilden, die das Hydrophob gleichförmig in den Teilchen dispergiert enthalten;
(c) Dispergieren der Polymerteilchen in einem hydrophilen Binder unter Bildung einer hydrophilen Zusammensetzung und
(d) Auftragen der hydrophilen Zusammensetzung auf einen Träger unter Bildung einer praktisch kristall- und agglomerationsfreien hydrophilen Schicht,
dadurch gekennzeichnet, daß mehr als 5 Gew.-% und bis zu 100 Gew.-% der Monomerenzusammensetzung aus mindestens einem ethylenisch ungesättigten, polymerisierbaren Monomer mit einer quervernetzbaren Gruppe bestehen, und daß das Monomer während der Polymerisation quervernetzt wird.
20. Verfahren nach Anspruch 19, in dem eine strahlungsempfindliche Schicht über der hydrophilen Schicht angeordnet wird.
21. Verfahren nach Anspruch 19, in dem als Hydrophob ein optischer Aufheller verwendet wird.
22. Verfahren nach Anspruch 19, in dem die Stufe (a) bei einer Temperatur ausgeführt wird, die über Raumtemperatur liegt, aber geringer als die Temperatur ist, bei der eine spontane Polymerisation der Monomeren erfolgt.
23. Verfahren nach Anspruch 19, in dem als hydrophiler Binder Gelatine verwendet wird.
24. Verfahren nach Anspruch 19, in dem ein oleophiles oberflächenaktives Mittel und ein oleophiler Polymerisationsinitiator in den Monomeren vor der Polymerisation gelöst werden.
25. Verfahren nach Ansprüchen 19 bis 24, in dem das ethylenisch ungesättigte polymerisierbare Monomer Styrol, das ethylenisch ungesättigte polymerisierbare Monomer mit einer quervernetzbaren Gruppe Divinylbenzol, der hydrophile Binder Gelatine und das Hydrophob 2,5-Bis(6-butyl)-2-benzoxazolyl)thiophen ist.
EP87903494A 1986-05-01 1987-04-17 Aufzeichnungselemente mit hydrophilen schichten, die hydrophobe in polymerteilchen enthalten, und methode zu ihrer herstellung Expired - Lifetime EP0266410B1 (de)

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US4203716A (en) * 1976-11-24 1980-05-20 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
CA1248387A (en) * 1983-12-16 1989-01-10 Herbert D. Remley Elements having hydrophilic layers containing hydrophobes in polymer particles and a method of making same

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Research Disclosure , no. 157 , May 1977 ,(Havant,Hampshire,GB ),L.R.Hamilton et al .:"Photographic emulsion layers containing color-forming couplers ", page 4, disclosure no. 15713 see the whole disclosure *

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